Described herein is a composition and method for the formation of a boron containing film or a boron-doped silicon containing film. More specifically, described herein are compounds, and composition and method comprising same, for formation of a stoichiometric or a non-stoichiometric boron-containing film or material, or a boron-doped silicon containing film at one or more deposition temperatures.
Boron compounds are needed, for example, in the fabrication of fin field effect transistors (FinFET) or other application in semiconductor industrial. Thus far, boron precursors such as boron halides (e.g., BCl3), trialkylborane, or boron alkoxide precursors have been used for boron doped films.
The reference entitled “Silyl-amino boron compounds”, Burg, A. B. and et al., J. Am. Chem. Soc., Vol. 72: pp. 3103-3107, describes the formation of various boron compounds.
U.S. Pat. Nos. 8,288,292 and 8,479,683 describe a method of forming a boron nitride or boron carbon nitride dielectric that produces a conformal layer without a loading effect. The dielectric layer is formed by chemical vapor deposition (CVD) of a boron-containing film on a substrate, at least a portion of the deposition being conducted without plasma, and then exposing the deposited boron-containing film to a plasma. The CVD component dominates the deposition process, producing a conformal film without loading effect. The dielectric is ashable, and can be removed with a hydrogen plasma without impacting surrounding materials. The dielectric has a much lower wet etch rate compared to other front end spacer or hard mask materials such as silicon oxide or silicon nitride, and has a relatively low dielectric constant, much lower then silicon nitride.
US Publ. No. 2013/052836A describes a method for manufacturing a semiconductor device, including forming an insulating film having a prescribed composition and a prescribed film thickness on a substrate by alternately performing the following steps prescribed number of times: supplying one of the sources of a chlorosilane-based source and an aminosilane-based source to a substrate in a processing chamber, and thereafter supplying the other source, to form a first layer containing silicon, nitrogen, and carbon on the substrate; and supplying a reactive gas different from each of the sources, to the substrate in the processing chamber, to modify the first layer and form a second layer.
The reference entitled “Transition Metal-Catalyzed Formation of Boron-Nitrogen Bonds: Catalytic Dehydrocoupling of Amine-Borane Adducts to Form Aminoboranes and Borazines” J. Am. Chem. Soc. 125(31): 9424-9434 describes a method to make aminoboranes and borazine derivatives from either primary or secondary amine-borane adducts using late transition metal complexes as precatalysts.
U.S. Pat. No. 8,753,717 describes a film forming method for forming a thin film including boron, nitrogen, silicon, and carbon on a surface of a processing target by supplying a boron containing gas, a nitriding gas, a silane-based gas, and a hydrocarbon gas in a processing container in which the processing target is accommodated to be vacuum sucked includes: a first process which forms a boron nitride (BN) film by performing a cycle of alternately and intermittently supplying the boron-containing gas and the nitriding gas once or more; and a second process which forms a silicon carbonitride (SiCN) film by performing a cycle of intermittently supplying the silane-based gas, the hydrocarbon gas, and the nitriding gas once or more.
U.S. Publ. No. 2013/239893 describes a method for stabilizing a film forming apparatus, which can selectively perform a boron-containing nitride film forming process or a non-boron-containing nitride film forming process on at least one target object to be processed in a vacuum-evacumable processing chamber, the method includes performing a heat stabilization process to heat the interior of the processing chamber under an oxygen-containing gas atmosphere, between the boron-containing nitride film forming process and the non-boron-containing nitride film forming process when the non-boron-containing nitride film forming process is performed after the boron-containing nitride film forming process.
U.S. Pat. Nos. 6,815,350 and 6,962,876 describe a method for forming a ternary thin film using an atomic layer deposition (ALD) process includes supplying a first and a second reactive material to a chamber containing a wafer, the first and second reactive materials being adsorbing on a surface of the wafer, supplying a first gas to the chamber to purge the first and second reactive materials that remain unreacted, supplying a third reactive material to the chamber to cause a reaction between the first and second reactive materials and the third reactive material to form a thin film monolayer, supplying a second gas to purge the third reactive material that remains unreacted and a byproduct, and repeating the above steps for forming the thin film monolayer a predetermined number of times to form a ternary thin film having a predetermined thickness on the wafer. Preferably, the ternary thin film is a silicon boronitride (SiBN) film.
U.S. Pat. No. 7,633,125 describes the integration of silicon boron nitride in high voltage semiconductors. In one example, a microelectronic apparatus includes a semiconductor substrate upon which transistors of an integrated circuit are formed, a plurality of transistor gates formed upon the semiconductor substrate, a gate spacer dielectric disposed between the gates, and a contact etch stop dielectric disposed upon the gates and gate spacer dielectric, the contact etch stop dielectric comprising SiBN to reduce breakdown of the contact etch stop dielectric in high voltage applications.
U.S. Pat. No. 8,324,014 describes the deposition of boron compounds on substrates by chemical vapor deposition (CVD) or physical vapor deposition (PVD) using a boron compound precursor of general structure R1R2R3B (R1=H, C1-5-alkyl, aryl, alkylamide, —OH, C1-5-alkoxy; R2 and R3 is a group that contains boron and can comprise a saturated 6-membered heterocyclic compd. (e.g., containing 3 atoms of B and 3 atoms of N), optionally substituted with C1-5-alkyl, aryl, alkylamide and C1-5-alkoxy (esp. tri-Me borate or tri-iso-Pr borate)). Specifically, the compounds can be hexa-substituted borazines, 1,3,5-tri-substituted borazines, or 2,4,6-trisubstituted borazines (esp. 1,3,5-trimethylborazine). The boron can be deposited in the presence of added material that can act as dopants for solar cell layers.
U.S. Pat. No. 3,031,503 describes the preparation of aminoboranes compounds from tetraboranes according to the following equation: 2 R2NH+B4H10→2R2NB2H5+H2 at 150-180°.
U.S. Pat. No. 8,679,958 describes the deposition of dopant films, such as doped silicon oxide films, by atomic layer deposition processes. In some embodiments, a substrate in a reaction space is contacted with pulses of a silicon precursor and a dopant precursor, such that the silicon precursor and dopant precursor adsorb on the substrate surface. Oxygen plasma is used to convert the adsorbed silicon precursor and dopant precursor to doped silicon oxide.
The disclosure of the foregoing patents, applications and literature is hereby incorporated by reference.
Thus, there is still a need to develop a process for forming a boron-containing film or a boron-doped silicon containing film using one or more boron compound in a chemical vapor deposition (CVD), an atomic layer deposition (ALD), or a plasma enhanced atomic layer deposition (ALD) process or a plasma enhanced ALD-like process.